WO2024090696A1 - Appareil d'élimination d'additif et procédé d'élimination d'additif utilisant celui-ci - Google Patents

Appareil d'élimination d'additif et procédé d'élimination d'additif utilisant celui-ci Download PDF

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WO2024090696A1
WO2024090696A1 PCT/KR2023/006793 KR2023006793W WO2024090696A1 WO 2024090696 A1 WO2024090696 A1 WO 2024090696A1 KR 2023006793 W KR2023006793 W KR 2023006793W WO 2024090696 A1 WO2024090696 A1 WO 2024090696A1
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Prior art keywords
polymer
solvent
swelling
inlet
injection port
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PCT/KR2023/006793
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English (en)
Korean (ko)
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김준식
박종서
오현택
이상호
김도담
강주형
유진숙
차선철
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주식회사 엘지화학
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Priority to EP23866594.7A priority Critical patent/EP4393672A1/fr
Priority to CN202380014094.5A priority patent/CN118265597A/zh
Publication of WO2024090696A1 publication Critical patent/WO2024090696A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/02—Recovery or working-up of waste materials of solvents, plasticisers or unreacted monomers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0293—Dissolving the materials in gases or liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/20—Waste processing or separation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to an additive removal device for removing additives contained in a polymer for recycling of the polymer and an additive removal method using the same.
  • polyvinyl chloride has hard or soft characteristics, excellent molding processability, and excellent price competitiveness, so it is applied to various fields of application due to its general utility.
  • polyvinyl chloride resin cannot be used alone, and is used mixed with a plasticizer to achieve various physical properties, such as providing flexibility to polyvinyl chloride resin and improving physical properties such as processability.
  • phthalate-based plasticizers which were previously used as plasticizers, are harmful to the environment and the human body and are subject to severe domestic and foreign regulations. Therefore, if the phthalate-based plasticizers are not removed in order to recycle polymers such as existing polyvinyl chloride resins in which these phthalate-based plasticizers are used, they cannot be commercialized. There was a problem that was difficult to solve. Therefore, recently, attempts have been made to effectively remove the phthalate plasticizer remaining in the recovered polymer in order to recycle the polymer in which the phthalate plasticizer was used.
  • the problem to be solved by the present invention is to solve the problems mentioned in the background technology of the above invention, to provide a continuous processing method that can remove the plasticizer contained in the polymer with high efficiency for recycling of the polymer, and , to provide a device for removing additives in polymers optimized for this purpose.
  • a barrel providing an internal space and having a polymer inlet on one side and a polymer outlet on the other side, a screw provided in the inner space of the barrel and rotating on an axis, and An additive comprising a solvent outlet at one end of the barrel, wherein the barrel is located between the polymer inlet and the polymer outlet, but includes a swelling solvent inlet adjacent to the polymer inlet and a shrinking solvent inlet adjacent to the polymer outlet.
  • a removal device is provided.
  • the present invention provides the steps of preparing the additive removal device, supplying a polymer containing an additive to the polymer inlet, supplying a swelling solvent and a shrinking solvent to the swelling solvent inlet and the shrinking solvent inlet, respectively, and supplying the supplied polymer. transferring the polymer to the outlet by rotating the screw shaft, swelling the polymer in the swelling zone from the polymer inlet to the swelling solvent inlet, and in the shrinkage zone from the swelling solvent inlet to the shrinking solvent inlet.
  • a method for removing additives including the step of shrinking the polymer is provided.
  • the additive removal device of the present invention enables continuous extraction of additives in polymers even with a small device size and a small amount of solvent used, and the additive removal efficiency can also be improved.
  • the polymer recovered from the waste resin is not dissolved in a solvent, but the swelling solvent is impregnated into the polymer to selectively diffuse and extract the additives inside the polymer. It is possible to remove additives from. Through this, the amount of solvent used can be reduced and the required equipment can be simplified, thereby improving economic efficiency.
  • FIG. 1 is a longitudinal cross-sectional view showing an additive removal device according to an embodiment of the present invention.
  • the additive removal device 1 includes a barrel 10 that provides an internal space and has a polymer inlet 20 on one side and a polymer outlet 30 on the other side, the barrel 10 It includes a screw 70 that is provided in the internal space and rotates on a shaft, and a solvent discharge portion 60 at one end of the barrel 10, and the barrel 10 has the polymer inlet 20 and the polymer It may include a swelling solvent inlet 40 located between the outlets 30 and adjacent to the polymer inlet, and a shrinking solvent inlet 50 adjacent to the polymer outlet.
  • the polymer is a polymer recovered from waste resin, obtained by pre-treating waste resin, and may be in the form of particles. Meanwhile, the waste resin, regardless of whether it is hard or soft, can be recovered from various products or uses molded using the resin or its composition. Additionally, the recovered polymer may be a single type of polymer, or may be a resin composition blended with other resins.
  • the pretreatment refers to all processes of treating waste resin with a polymer in a state suitable for application to the additive removal device of the present invention.
  • the pretreatment may be a process of removing relatively large foreign substances such as dust by first washing the waste resin with a solvent such as water, drying it, and then pulverizing it into particles.
  • the average particle diameter (D50) of the polymer may be 0.1 mm or more and 2 mm or less.
  • D50 the average particle diameter of the recovered polymer decreases, the impregnation solvent impregnation rate increases, thereby increasing the additive removal rate.
  • the processing time increases to produce the recovered polymer with a small average particle diameter.
  • the type of polymer suitable for application to the additive removal device according to an embodiment of the present invention is not particularly limited, but if the additive removed by the additive removal device is a plasticizer, the polymer may be polyvinyl chloride (PVC). there is.
  • PVC polyvinyl chloride
  • additives such as plasticizers, fillers, flame retardants, stabilizers, fillers, foaming agents, viscosity lowering agents, colorants, and heat stabilizers are used to provide the desired physical properties to the resin during the product manufacturing process, such as during polymerization of the polymer or during molding after polymerization. may be used, and the additives used remain in the resin prepared depending on the additives. Therefore, the above additives may also be included in waste resin recovered from products for resin recycling.
  • additives may be difficult to manufacture recycled polymers with good physical properties.
  • the influence of the above additives may result in deterioration of physical properties such as deformation of the recycled polymer or deterioration of surface properties, or deterioration of color characteristics such as discoloration.
  • the additive that needs to be removed from the recovered polymer containing the additive may mainly be a plasticizer.
  • the plasticizer may be a phthalate-based plasticizer.
  • the phthalate plasticizer includes dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl terephthalate (DOTP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and di-( It may be one or more of 2-ethylhexyl) terephthalate (DEHTP) and butylbenzel phthalate (BBP).
  • DOP dioctyl phthalate
  • DBP dibutyl phthalate
  • DDP dioctyl terephthalate
  • DINP diisononyl phthalate
  • DIDP diisodecyl phthalate
  • It may be one or more of 2-ethylhexyl) tere
  • the additive removal method according to an embodiment of the present invention selectively elutes only the additive while maintaining the shape of the polymer, using a conventional method of dissolving the polymer itself using a soluble solvent and then recrystallizing it.
  • This existing solution-recrystallization method is difficult to remove in the case of additives such as plasticizers that have good compatibility with the resin.
  • it requires the use of an excessive amount of solvent (anti-solvent), which increases not only the cost of the solvent but also the cost of refining it. Therefore, there is a disadvantage in that the purification efficiency is low compared to the cost.
  • the additive removal method of the present invention first contacts the polymer containing the additive with a swelling solvent to impregnate the swelling solvent into the polymer to swell the polymer, and at the same time removes the additive from the polymer by diffusing the additive in the polymer into the swelling solvent. can do.
  • the polymer impregnated with the swelling solvent is contracted by contacting it with a shrinking solvent, thereby minimizing the content of the solvent present in the polymer. That is, as the polymer in a swollen state is contracted by the shrinkage solvent, the swelling solvent containing the internal additives is discharged out of the polymer as much as possible, ultimately reducing the additive content in the polymer.
  • immersion refers not only to washing of additives (plasticizers) present on the surface of the recovered polymer by the impregnation solvent, but also to the impregnation solvent penetrating into the recovered polymer by diffusion, This means eluting the additive (plasticizer).
  • the present invention is an optimal method that allows the additive removal method to be performed continuously and reduces the amount of swelling and shrinking solvents used, thereby increasing economic efficiency and simultaneously improving the removal efficiency of additives, specifically plasticizers. It is intended to provide an additive removal device (1).
  • the barrel 10 is an element constituting the body of the additive removal device 1, and may be of a tubular shape extending in the longitudinal direction and having an internal space.
  • the array 10 may be made of a material that is not deformed by a solvent, which will be described later, and may specifically be made of metal or glass.
  • the polymer supplied to the polymer inlet 20 is transported to the polymer outlet 30 by the screw 70, and the solvent supplied to the swelling solvent inlet 40 and the shrinking solvent inlet 50 is moved by gravity.
  • the space transported by the polymer may refer to the space where additives contained in the polymer are removed due to swelling and contraction of the polymer.
  • the barrel 10 may be provided with a polymer inlet 20 on one side and a polymer outlet 30 on the other side.
  • the polymer may be a polymer containing an additive, and the polymer may be supplied to the polymer injection port 20 and the internal additive may be removed through a process of sequentially contacting a swelling solvent and a shrinking solvent, which will be described later.
  • the polymer can be discharged through the polymer outlet 30.
  • the additive removal device 1 may include a screw 70 that is provided in the inner space of the barrel 10 and rotates on an axis, and the additive removal device 1 may include a screw 70 of the barrel 10 to provide rotational force to the screw 70.
  • the other end may include a rotational force supply device 80.
  • the other end may be an end adjacent to the polymer discharge port 30 among the ends of the barrel 10.
  • the rotational force supply device 80 is used to supply driving force for shaft rotation to the screw 70 and may specifically be a motor.
  • the screw 70 is connected to the rotational force supply device 80 and is fixed to the shaft 71 that rotates and the outer peripheral surface of the shaft 71 and extends spirally along the longitudinal direction of the shaft 71. It may include a plate 72.
  • the plate 72 can be rotated using the shaft 71 as a rotation axis by the rotational force provided by the rotational force supply device 80. Through this, the polymer supplied to the polymer inlet 20 is loaded on the plate 72 and can be continuously transferred to the polymer outlet 30 by the axis rotation of the screw 70.
  • the supply flow rate (g/min) of the polymer supplied to the polymer injection port 20 is the volume of 1 pitch (p) of the screw (cm 3 ), the bulk density of the supplied polymer (g/cm 3 ), and the screw. It can be determined in relation to the rotation speed (RPM, min -1 ), and specifically, it can satisfy General Equation 1 below.
  • the additive removal device 1 may be disposed along an extension of the central axis of rotation of the screw 70, specifically, an extension of the shaft 71 at an angle to the ground. That is, the surface height of the polymer discharge port 30 may be placed higher than the surface height of the polymer injection port 20.
  • the length of the pedestal supporting the polymer outlet 30 side is made longer than the length of the pedestal supporting the polymer inlet 20 side, so that the extension line of the central axis of rotation of the screw 70 and The inclination angle (z) with the ground can be implemented.
  • the swelling solvent and shrinking solvent introduced into the inner space of the barrel 10 due to the inclination angle (z) between the extension of the rotation center axis of the screw 70 and the ground will be transferred to the solvent discharge unit 60 by gravity.
  • the time for which the swelling solvent and shrinking solvent remain in the device and the time for which the solvent is in contact with the polymer can be determined. . Through this, additives in the polymer can be removed more efficiently.
  • the inclination angle (z) formed between the extension of the central axis of rotation of the screw 70 and the ground may be 5 degrees to 30 degrees.
  • the inclination angle (z) is also related to the flow rate of the supplied swelling solvent and pivoting solvent. If the inclination angle exceeds 30 degrees, the solvent supplied to the barrel 10 through the swelling solvent inlet 40 or the shrinking solvent inlet 50 is discharged without sufficiently remaining in the internal space of the barrel, that is, swelling the polymer. Alternatively, even though it has the ability to shrink, it is discharged in an excessively short period of time, so an excessive amount of solvent is required to be used more than necessary, and furthermore, there is a problem that the amount of energy required in the purification process for solvent reuse increases.
  • the inclination angle is less than 5 degrees, there is a high possibility that the solvent supplied to the barrel will be discharged to the polymer outlet 30 and lost, and also the solvent that has arrived adjacent to the solvent outlet, that is, the solvent in which the additive is concentrated, will flow smoothly into the solvent outlet. If it is not discharged properly, the removal efficiency of additives in the polymer may be reduced.
  • a swelling solvent may be supplied to the swelling solvent inlet 40, and a shrinkage solvent may be supplied to the shrinkage solvent inlet 50.
  • the internal space of the barrel 10 includes a swelling zone 100 from the polymer inlet 20 to the swelling solvent inlet 40 and a contraction from the swelling solvent inlet 40 to the shrinkage solvent inlet 50.
  • the swelling zone 100 is a cross section of the barrel 10 and includes a region from a cross section including the center of the polymer injection port 20 to a cross section including the center of the swelling solvent injection port 40.
  • the shrinkage zone 200 refers to a region from a cross section including the center of the swelling solvent injection port 40 to a cross section including the center of the shrink solvent injection port 50.
  • the polymer containing the additive supplied through the polymer inlet 20 is sequentially transferred to the swelling zone 100 and the shrinkage zone 200 in the process of being transferred to the polymer outlet 30 by the axial rotation of the screw 70. will pass through.
  • the distance (x) from the polymer injection port 20 to the swelling solvent injection port 40 may be the length of the swelling zone 100, and the distance from the swelling solvent injection port 40 to the shrinkage solvent injection port 50 (y) may be the length of the contraction zone 200.
  • the ratio (x/y) of the distance (x) from the polymer injection port 20 to the swelling solvent injection port 40 and the distance (y) from the swelling solvent injection port 40 to the shrinkage solvent injection port 50 is It may be 0.1 to 60, specifically 1 to 30. If the ratio (x/y) is less than 0.1, the time the polymer stays in the shrinkage zone becomes longer than necessary, which may reduce the economic feasibility of the process. If the ratio (x/y) is greater than 60, There is a problem in that the polymer in a swollen state has difficulty shrinking sufficiently because the residence time of the polymer in the shrinkage zone becomes shorter than necessary.
  • the polymer containing the additive comes into contact with the swelling solvent, so that the swelling solvent penetrates into the polymer, and the polymer swells while maintaining its unique molecular structure. It can be swollen.
  • the additives contained in the polymer are diffused by the impregnating solvent and eluted out of the recovered polymer, and the additives in the polymer can be removed.
  • the swelling solvent For efficient removal of additives from polymers, selection of a swelling solvent used for swelling of polymers is important. First, the swelling solvent must be able to be uniformly impregnated into the interior of the polymer particles at a high speed, and the maximum amount of additives contained in the polymer must be eluted into the swelling solvent impregnated within the polymer. Therefore, the swelling solvent must be selected in consideration of the type of polymer and the type of additive to be removed.
  • the swelling solvent is cyclohexanone, cyclopentanone, N, N-dimethyl acetamide, tetrahydrofuran, pyridine, 3-pentanone, 2-pentanone, dimethyl Formamide, methyl ethyl ketone, dichloromethane, 4-methylpentan-2-one, nitrobenzene, 1,4-dioxane, 1,1,2,2-tetrachloroethane, acetone, ethyl acetate, chloroform and dimethyl sulfoxide. It may be one or more of the sides, and specifically may be methyl ethyl ketone. In the case of the above solvent, not only can it be easily impregnated into the polymer, but it also has an excellent ability to elute additives within the polymer, such as phthalate-based plasticizers, so it can be preferably used.
  • the supply flow rate of the swelling solvent supplied to the swelling solvent inlet 40 ( cm 3 /min) can be determined depending on the supply flow rate of the polymer and the bulk density of the supplied polymer. Specifically, General Equation 2 below can be satisfied.
  • the residence time of the polymer in the swelling zone 100 can satisfy the general formula 3 below in relation to the value expressed by the average particle diameter (D50, mm) of the polymer.
  • the swelling solvent is impregnated into the polymer to sufficiently elute the additive.
  • the economic feasibility of the process may decrease. Specifically, when the rotational speed (RPM) of the screw is excessively lowered to increase the residence time, the yield of the polymer from which additives are obtained per unit time is reduced, or the length of the swelling zone 100 is increased to increase the residence time. In this case, the device size may be increased.
  • a mixed solvent of a swelling solvent and a shrinking solvent may exist in the swelling zone 100. That is, the shrinkage solvent supplied to the shrinkage solvent inlet 50 is discharged to the solvent discharge unit 60 through the shrinkage zone 200 and the swelling zone 100, so the swelling solvent and the shrinkage solvent are also discharged in the swelling zone 100. It comes into existence.
  • the flow rate of the swelling solvent and shrinkage solvent in the swelling zone 100 must be maintained at an appropriate ratio. must be controlled.
  • the respective flow rates of the swelling solvent and the shrinking solvent in the swelling zone 100 ultimately depend on the flow rate of the swelling solvent supplied to the swelling solvent inlet 40 and the flow rate of the shrinking solvent supplied to the shrinking solvent inlet 50. Therefore, it may be important to appropriately control the flow rate ratio for smooth impregnation of the swelling solvent and swelling of the polymer.
  • the flow rate ratio of the volumetric flow rate of the shrinking solvent supplied to the shrinking solvent inlet to the volumetric flow rate of the swelling solvent supplied to the swelling solvent inlet may be 30 vol% to 300 vol%.
  • the supply volume flow rate of the shrinkage solvent is supplied at 300% by volume or less of the supply volume flow rate of the swelling solvent, that is, when the swelling solvent is present in the swelling zone 100 in an amount more than 3 times the amount of the axis solvent, the polymer swelling of the swelling solvent The additive dissolution function may not be deteriorated.
  • the function of the shrinkage solvent in the shrinkage zone 200 and the resulting efficiency of removing additives in the polymer it is necessary to maintain the supply volume flow rate of the shrinkage solvent above a certain level, and therefore the volume flow rate of the swelling solvent If the flow rate ratio of the volumetric flow rate of the shrinkage solvent is less than 30% by volume, it may be difficult to smoothly implement the polymer shrinkage function in the shrinkage zone due to insufficient supply of the shrinkage solvent.
  • the polymer swollen by the swelling solvent may be transferred to the shrinkage zone 200 within the barrel 10.
  • the polymer swollen within the shrinkage zone 200 may be in contact with a shrinkage solvent.
  • the polymer transferred from the swelling zone 100 to the shrinking zone 200 is impregnated with a swelling solvent in which additives have been eluted, and when dried without removing the swelling solvent in the swollen polymer, the eluted polymer is Since the plasticizer remains inside the recycled polymer, the plasticizer removal efficiency decreases. Therefore, it is important to remove the swelling solvent inside the swollen polymer.
  • the solvent content and plasticizer content present in the swollen polymer can be minimized by shrinking the swollen polymer by chemical means using a shrinkage solvent. there is.
  • the shrinkage solvent is preferably a solvent that has a low degree of swelling of the polymer, and at the same time, when the additive is a phthalate-based plasticizer, a solvent that has a high degree of dissolving the phthalate-based plasticizer is preferable.
  • the shrinkage solvent is ethanol, toluene, cyclohexanol, isopropyl alcohol, benzene, cyclohexane, 1-pentanol, 1-butanol, 1-propanol, hexane, and dihydrogen. It may be one or more types of ethyl ether, and specifically may be isopropyl alcohol.
  • This shrinkage solvent not only can efficiently shrink the swollen polymer, but also has an excellent degree of dissolving the phthalate-based plasticizer, so that the plasticizer present inside the polymer can be easily removed from the polymer when the swollen polymer shrinks.
  • the supply flow rate of the supplied shrinkage solvent may be determined depending on the supply flow rate of the polymer and the bulk density of the supplied polymer. Specifically, General Equation 4 below can be satisfied.
  • the residence time of the polymer in the shrinkage zone 200 may be 0.5 to 10 minutes. If the residence time of the polymer in the shrinkage zone 200 is short, less than 0.5 minutes, the shrinkage solvent cannot sufficiently penetrate deep into the polymer, so shrinkage of the swollen polymer may not be smooth and the removal efficiency of additives may be reduced. In addition, if the residence time of the polymer in the shrinkage zone 200 is more than 10 minutes, the residence time becomes longer than necessary, making it uneconomical in terms of solvent usage and device size.
  • the shrunk polymer that has passed through the shrinkage zone 200 may be discharged to the outside of the additive removal device 1 through the polymer outlet 30.
  • the dryer in which the drying process is performed may be, for example, a paddle dryer, a floating bed dryer, a vacuum dryer, or a devolatilization extruder.
  • the swelling solvent and the shrinking solvent may be discharged through the solvent discharge unit 60.
  • the solvent outlet 60 may be coupled to the barrel 10 at one end of the barrel 10, and the solvent outlet 60 may include a solvent outlet.
  • the solvent discharge portion 60 may be separable from one end of the barrel 10 for cleaning the inside of the barrel 10.
  • the solvent discharged through the solvent discharge unit 60 may include a swelling solvent, a shrinkage solvent, and additives dissolved therein. Therefore, it is possible to perform a purification process to separate the swelling solvent, shrinkage solvent, and additives from the discharged solvent, and it is also possible to reuse each solvent and additives accordingly.
  • an additive manufacturing device 1 as shown in FIG. 1 was prepared.
  • the additive manufacturing device includes a barrel 10 with an inner diameter of 6 cm having a polymer inlet 20 on one side and a polymer outlet 30 on the other side, and a motor 80 at the other end of the barrel. It is provided, and a screw 70 connected to a motor is provided in the barrel.
  • the additive manufacturing device includes a swelling solvent inlet 40 and a shrinkage solvent inlet 50 between the polymer inlet and the polymer outlet.
  • the ratio (x/y) of the distance (x) from the polymer injection port to the swelling solvent injection port and the distance (y) from the swelling solvent injection port to the shrinking solvent injection port was 4.
  • a polymer powder sample containing PVC recovered polymer (D50: 200 ⁇ m) containing 14.3% by weight of phthalate plasticizer was prepared, and methyl ethyl ketone (MEK) as a swelling solvent and isopropyl alcohol (IPA) as a shrinking solvent were used. Ready. Then, MEK was injected into the swelling solvent inlet 40 at a volume flow rate of 15.5 cm 3 /min (0.75 kg/hr as a mass flow rate), and IPA was injected into the shrinking solvent inlet 50 at a volume flow rate of 10.6 cm 3 /min (at a mass flow rate of 0.75 kg/hr).
  • MEK methyl ethyl ketone
  • IPA isopropyl alcohol
  • GC-FID gas chromatography flame ionization detection analysis
  • Example 2 Compared to Example 1, MEK was flowed through the swelling solvent inlet 40 at a volume flow rate of 7.5 cm 3 /min (mass flow rate of 0.375 kg/hr), and IPA was flowed through the shrinking solvent inlet 50 at a flow rate of 2.7 cm 3 /min.
  • the plasticizer in the PVC polymer was removed using the same apparatus and method as in Example 1, except that each was supplied at a volume flow rate of min (0.125 kg/hr as a mass flow rate).
  • the residual plasticizer concentration of the discharged PVC polymer was measured in the same manner as in Example 1, and the result was 250ppm.
  • Example 1 Compared to Example 1, no solvent was supplied to the swelling solvent inlet 40, and MEK, a swelling solvent, was supplied only to the shrinkage solvent inlet 50 at a rate of 25.9 cm 3 /min (mass flow rate of 1.25 kg/hr).
  • MEK a swelling solvent
  • the plasticizer in the PVC polymer was removed using the same device and method as in Example 1, except that the residence time of the polymer in the device was 30 minutes.
  • the residual plasticizer concentration of the discharged PVC polymer was measured in the same manner as in Example 1, and the result was 4,200 ppm.
  • Comparative Example 1 Compared to Comparative Example 1, the same device and method as Comparative Example 1 were used, except that IPA, a shrinkage solvent, was supplied at 26.5 cm 3 /min (mass flow rate of 1.25 kg/hr) only through the shrinkage solvent inlet 50. Plasticizers in PVC polymer were removed.
  • IPA a shrinkage solvent
  • the residual plasticizer concentration of the discharged PVC polymer was measured in the same manner as in Example 1, and the result was 62,000 ppm.
  • a mixed solvent in which MEK, a swelling solvent, and IPA, a shrinkage solvent, were mixed at a weight ratio of 1:1 was used only through the shrinkage solvent inlet 50 at a flow rate of 26.0 cm 3 /min (1.25 kg/hr as a mass flow rate).
  • the plasticizer in the PVC polymer was removed using the same device and method as in Comparative Example 1, except that it was supplied as .
  • the residual plasticizer concentration of the discharged PVC polymer was measured in the same manner as in Example 1, and the result was 1,400 ppm.

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Abstract

La présente invention concerne un appareil d'élimination d'additif comprenant : un cylindre qui fournit un espace interne et a une entrée de polymère au niveau d'un côté et une sortie de polymère au niveau de l'autre côté ; une vis qui est disposée dans l'espace interne du cylindre et tourne axialement ; et une partie d'évacuation de solvant qui est disposée au niveau de l'extrémité du cylindre, le cylindre comprenant une entrée de solvant de gonflement et une entrée de solvant de retrait qui sont situées entre l'entrée de polymère et la sortie de polymère, l'entrée de solvant de gonflement étant adjacente à l'entrée de polymère, et l'entrée de solvant de retrait étant adjacente à la sortie de polymère.
PCT/KR2023/006793 2022-10-27 2023-05-18 Appareil d'élimination d'additif et procédé d'élimination d'additif utilisant celui-ci WO2024090696A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP23866594.7A EP4393672A1 (fr) 2022-10-27 2023-05-18 Appareil d'élimination d'additif et procédé d'élimination d'additif utilisant celui-ci
CN202380014094.5A CN118265597A (zh) 2022-10-27 2023-05-18 添加剂去除装置和使用该装置去除添加剂的方法

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JPH1045941A (ja) * 1996-08-07 1998-02-17 Chiyoda Corp プラスチック廃棄物の分別方法及び装置
JP2006009033A (ja) * 2002-03-20 2006-01-12 Matsushita Electric Ind Co Ltd 抽出装置
JP2007146176A (ja) * 2001-03-01 2007-06-14 Matsushita Electric Ind Co Ltd 添加剤を含む熱可塑性樹脂組成物の処理装置
KR20070109317A (ko) * 2006-05-10 2007-11-15 현대자동차주식회사 폴리비닐클로라이드에 함유된 가소제의 분리 및 분석 방법
KR20200105317A (ko) * 2019-02-28 2020-09-07 주식회사 엘지화학 가소제의 회수 방법

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KR100923535B1 (ko) 2007-11-21 2009-10-27 금호석유화학 주식회사 테이퍼드된 블록 공중합체를 함유한 개질 아스팔트 조성물

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1045941A (ja) * 1996-08-07 1998-02-17 Chiyoda Corp プラスチック廃棄物の分別方法及び装置
JP2007146176A (ja) * 2001-03-01 2007-06-14 Matsushita Electric Ind Co Ltd 添加剤を含む熱可塑性樹脂組成物の処理装置
JP2006009033A (ja) * 2002-03-20 2006-01-12 Matsushita Electric Ind Co Ltd 抽出装置
KR20070109317A (ko) * 2006-05-10 2007-11-15 현대자동차주식회사 폴리비닐클로라이드에 함유된 가소제의 분리 및 분석 방법
KR20200105317A (ko) * 2019-02-28 2020-09-07 주식회사 엘지화학 가소제의 회수 방법

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